Oxime carbamates

ABSTRACT

Novel oxime-carbamates of the formula ##SPC1## 
     Wherein 
     R 1  is --CH 3 , --CH(CH 3 ) 2 , ##EQU1## --C(CH 3 ) 3 , or --C 6  H 5  ; R 2  is --H or --CH 3  ; 
     R 3  is --CH 3 , --CH 2  CH 3 , --(CH 2 ) 2  CH 3 , --(CH 2 ) 3  CH 3 , --CH 2  CH 2  Cl or --C 6  H 5  ; 
     R 4  is --H, --CH 3 , --CH 2  CH 3 , --(CH 2 ) 2  CH 3 , --CH(CH 3 ) 2 , --(CH 2 ) 3  CH 3 , --CH 2  CH=CH 2 , --CH 2  C.tbd.CH, --C 6  H 5 , ##EQU2## --CH (OH)CCl 3 , --CH 2  CH 2  X 1 , where X 1  is --Cl, --Br, --NH 2 , --OH, --OCOCH 3 , --OCOCH 2  Cl, or --OCONHCH 3  ; 
     R 5  and R 6  are each --H or --CH 3 , with the proviso that when R 5  and R 6  are both CH 3  then both CH 3  groups may be on either the same carbon atom or on different carbon atoms; 
     R 7  is H, --CH 3  or --CH 2  C 6  H 5  ; 
     X 2  is --Cl, --Br or --I; and 
     n is O or 1, with the proviso that when n is 1 then N 
     bears a + charge and X 2  bears a - charge. 
     These compounds are useful as insecticides and acaricides.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel oxime-carbonates and their use asinsecticides and acaricides.

2. Description of the Prior Art

A number of carbamates are known to exhibit insecticidal properties.Included among these are the following currently available in commerce:##SPC2##

In addition, there is also a limited number of oxime-carbamates in use,such as, for example:Compound U.S. Patent No.Trademark______________________________________CH₃ S∠C=NOCONHCH₃METHOMYLCH₃CH₃|CH₃ SCC=NOCONHCH₃ 3,217,037TEMIK|||H|CH₃______________________________________

However, the present oxime-carbamates, which may also be described asdihydropyrazinone oxime carbamates are novel compounds which displayexceptional insectidical activity.

SUMMARY OF THE INVENTION

The present invention relates to novel oxime-carbamates and to the useof these compounds in the control of insects and acarids. The compoundsof particular interest are those represented by the formula ##SPC3##

Where

R₁ is --Ch₃, --CH(CH₃)₂, ##EQU3## --C(CH₃)₃, or --C₆ H₅ ; R₂ is --H or--CH₃ ;

R₃ is --CH₃, --CH₂ CH₃, --(CH₂)₂ CH₃, --(CH₂)₃ CH₃, --CH₂ CH₂ Cl or --C₆H₅ ;

R₄ is --H, --CH₃, --CH₂ CH₃, --(CH₂)₂ CH₃, --CH(CH₃)₂, --(CH₂)₃ CH₃,--CH₂ CH=CH₂, --CH₂ C.tbd.CH, --C₆ H₅, ##EQU4## --CH(OH)CCl₃, --CH₂ CH₂X₁, whereas X₁ is --Cl, --Br, --NH₂, --OH, --OCOCH₃, --OCOCH₂ Cl, or --OCONHCH₃ ; R₅ and R₆ are each --H or --CH₃, with the proviso that whenR₅ and R₆ are both CH₃ then both CH₃ groups may be on either the samecarbon atom or on different carbon atoms.

R₇ is --H, --CH₃ or --CH₂ C₆ H₅ ;

X₂ is --Cl, --Br or --I; and

n is 0 or 1, with the proviso that when n is 1 then N

bears a + charge and X₂ bears a - charge.

The present invention also provides a method for the control of insectand acarid infestation which comprises applying either to the locus ofsaid infestation, or systematically, a pesticidally effective amount ofan oxime-carbamate having the formula ##SPC4##

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, X₂ and n have the meaningshereinbefore disclosed.

Illustrative examples of the oxime-carbamates encompassed within theabove described general formula are the following compounds: (Note --the ##EQU5## group is indicated as ) ##SPC5##

As hereinbefore stated, the compounds of the present invention areuseful as insecticides and acaricides. They are conveniently applied tothe locus of infestation in a variety of ways, for example, as asolution in an organic solvent, as an emulsion, as a spray, on an inertcarrier such as clay, kaolin, talc, bentonite, attapulgite, ordiatomaceous earth and the like, or as a formulated product in liquid orsolid form. The present compounds may also be applied systemically inthe same variety of ways. Useful organic solvents are the aromatics suchas toluene, xylene, benzene, cyclohexane, and alkylated coal tardistillates, aliphatics such as naphthas and petroleum distillates, andvarious combinations of alcohols, esters, ketones and chlorinatedcompounds. The present insecticides may be provided as concentratedwettable powders containing as much as 80-90% active ingredient, or asconcentrates in solid, liquid, or paste form containing 25-75% by weightof toxicant which may be diluted for application as desired, or asformulated products containing as little as about 5-10% activeingredient.

PREPARATION

The oxime-carbamates of this invention are prepared by utilizing thefollowing general reaction employing the indicated reactants: ##SPC6##

where R₁, R₂, R₃, R₄, R₅ and R₆ have the meanings hereinbeforedescribed.

By varying Reactant B so that R₅ and R₆ are on the same or adjacentcarbon atoms, it is possible to prepare compounds in which R₅ and R₆ areon the same or adjacent carbon atoms.

Reactants A (Chloro-oxime carbamates) are conveniently prepared by knownmethods. Reactants B (ethylenediamines), may be utilized as either thedihydrochloride salts or as the free bases. They too are prepared byknown methods or purchased commercially.

The foregoing General Reaction is illustrated by Example 1 whichdescribes the preparation of Compound No. 1.

EXAMPLE 1

A solution of 20 g. (0.112 mole) of1-acetyl-1-chloroformaldoxime-N-methylcarbamate (Reactant A) in 200 ml.methanol was stirred in an ice bath while 13.4 g. (0.224 mole) ofethylenediamine (Reactant B) was added. After stirring for 30 minutes atambient temperature, the reaction mixture was evaporated to drynessunder reduced pressure. Chloroform (200 ml.) was added and theprecipitated ethylenediamine hydrochloride removed by filtration. Thefiltrate was evaporated to dryness and the residue extracted withboiling ethyl acetate. The extract was evaporated and the extractionprocess repeated with benzene. Cooling of the hot benzene extract andfiltration provided 13.1 g. (63%) of Compound No. 1 as a light yellowsolid, m.p. 129°-130°C.

EXAMPLES 2-7

The following table, Table 1, summarizes the preparation of CompoundNos. 2-7 by the same procedure as set forth in Example 1, with theexception that the reactants A and B were varied as indicated.

                                      Table 1                                     __________________________________________________________________________    Reactants                   Product                                           Example                                                                              A           B        (Compound No.)                                    __________________________________________________________________________         OCl                                                                           ∥|                                                     2    CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                         H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2                                                    2                                                      OCl                                                                           ∥|                                                     3    CH.sub.3 C--C=NOCONH(CH.sub.2).sub.2 CH.sub.3                                               "        3                                                      OCl                                                                           ∥|                                                     4    CH.sub.3 C--C=NOCONHC.sub.6 H.sub.5                                                         "        4                                                      OCl                                                                           ∥|                                                     5    (CH.sub.3).sub.2 CHC--C=NOCONHCH.sub.3                                                      "        5                                                      0Cl                                                                           ∥|                                                     6    C--C--NOCONHCH.sub.3                                                                        "        6                                                      O Cl                                                                          ∥|                                                     7    C.sub.6 H.sub.5 C--C=NOCONHCH.sub.3                                                         "        7                                                 __________________________________________________________________________

In those instances where the product does not solidify, it is purifiedby silica gel chromatography.

EXAMPLE 8

Compound No. 11 was prepared in the following manner: A solution of 5.0g. (0.028 mole) of 1-acetyl-1-chloroformaldoxime-N-methylcarbamate(Reactant A) in 20 ml. of chloroform (or methanol) was added to astirred mixture of 2.47 g. (0.028 mole) of N-ethylethylenediamine(Reactant B) and 10 g. of anhydrous potassium carbonate in 30 ml. ofchloroform at 5°-10°C. The reaction was stirred 4 hours at roomtemperature, 2 g. of magnesium sulfate was added and the mixturefiltered. The filtrate was evaporated to dryness giving 7.4 g. of an oilwhich was redissolved in chloroform, washed with water, and dried overmagnesium sulfate. After removal of the solvent, the solid was slurriedin petroleum ether to give 4.75 grams (80%) of Compound No. 11 as acream-colored solid, mp 68°-72°C. In those instances where the productdoes not solidify, it is purified by column chromatography.

EXAMPLES 9-28

The following table, Table 2, summarizes the preparation of CompoundNos. 8-10, 12-18, 30-34, 40-44, and 52 by the procedure set forth inExample 8, except that the Reactants A and B were varied as indicated.

                                      Table 2                                     __________________________________________________________________________    Reactants                            Product                                  Example                                                                              A                B            (Compound No.)                           __________________________________________________________________________         OCl              NH.sub.2                                                     ∥|                                                                           |                                               9   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   CH.sub.3 CHCH.sub.2 NH.sub.2                                                                 8                                                              NH.sub.2                                                                      |                                              10     "              (CH.sub.3).sub.2 C--CH.sub.2 NH.sub.2                                                        9                                             0Cl                                                                           ∥|                                                     11   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   CH.sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2                                                        10                                            OCl                                                                           ∥|                                                     12   CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                            CH.sub.3 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2                                               12                                            OCl                                                                           ∥|                                                     13   CH.sub.3 C--C=NOCONHCH.sub.2 CH.sub.3                                                            "            13                                            OCl                                                                           ∥|                                                     14   CH.sub.3 C--C=NOCONH(CH.sub.2).sub.2 CH.sub.3                                                    "            14                                            OCl                                                                           ∥|                                                     15   CH.sub.3 C--C=NOCONHCH.sub.2 CH.sub.2 Cl                                                         "            15                                            OCl                                                                           ∥|                                                     16   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   CH.sub.3 (CH.sub.2).sub.2 NHCH.sub.2 CH.sub.2                                 NH.sub.2       16                                       17     "              (CH.sub.3).sub.2 CHNHCH.sub.2 CH.sub.2 NH.sub.2                                              17                                            OCl                                                                           ∥|                                                     18   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   CH.sub.3 (CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2                                 NH.sub.2       18                                            O Cl                                                                          ∥|                                                     19   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   H.sub.2 NCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2                                NH.sub.2       30                                            OCl                                                                           ∥|                                                     20   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   HOCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2                                             31                                            OCl                                                                           ∥|                                                     21   CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                              "            32                                            OCl                                                                           ∥|                                                     22   CH.sub.3 C--C=NOCONH(CH.sub.2).sub.3 CH.sub.3                                                    "            33                                            OCl                                                                           ∥|                                                     23   C-- C=NOCONHCH.sub.3                                                                             "            34                                            OCl                                                                           ∥|                                                     24   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   CH.sub.2 =CHCH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2                                            40                                            OCl                                                                           ∥|                                                     25   CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                            CH.sub.2 =CHCH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2                                            41                                            OCl                                                                           ∥|                                                     26   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   CH.tbd.CCH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2                                                42                                            OCl                                                                           ∥|                                                     27   CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                              "            43                                            OCl                                                                           ∥|                                                     28   CH.sub.3 C--C=NOCONHCH.sub.3                                                                   C.sub.6 H.sub.5 NHCH.sub.2 CH.sub.2 NH.sub.2                                                 44                                            OCl                                                                           ∥|                                                     28A  CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                            CH.sub.3 CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2                                NH.sub.2       52                                       __________________________________________________________________________

EXAMPLE 29

Compound No. 19 was prepared in the following manner: A suspension of5.0 g. (0.028 mole) of 1-acetyl-1-chloroformaldoxime-N-methylcarbamate(Reactant A), 5.75 g. (0.029 mole) of N-(2-chloroethyl)-ethylenediaminedihydrochloride (Reactant B) and 2.5 g of magnesium sulfate in 30 ml. oftetrahydrofuran was stirred at 5°-10°C. and treated slowly with asolution of 12.5 ml. of triethylamine in 20 ml. of tetrahydrofuran.After the addition was completed, the reaction mixture was stirred 4hours at room temperature, filtered and the filtrate evaporated todryness giving 6.8 g. (98.5%) of oil which solidified on standing. Thecrude product was purified by redissolving in chloroform, washing withwater, drying over magnesium sulfate, concentrating and slurrying theresulting solid with diethyl ether to give 3.9 g. (57%) of Compound No.19 as a light yellow solid, m.p. 98°-100°C.

EXAMPLES 30-39

Compounds 20-29 were prepared according to the procedure set forth inExample 29, except that the Reactants A and B were varied as indicatedin Table 3.

                                      Table 3                                     __________________________________________________________________________    Reactants                             Product                                 Example                                                                              A              B               (Compound No.)                          __________________________________________________________________________         OCl                                                                           ∥|                                                     30   CH.sub.3 --C--C=NOCONHCH.sub.3                                                                 ClCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2.2HC                          l               20                                           OCl                                                                           ∥|                                                     31   CH.sub.3 --C--C=NOCONHCH.sub.2 CH.sub.3                                                        "               21                                           OCl                                                                           ∥|                                                     32   CH.sub.3 --C--C=NOCONH(CH.sub.2).sub.2 CH.sub.3                                                "               22                                           OCl                                                                           ∥|                                                     33   CH.sub.3 --C=C=NOCONH(CH.sub.2).sub.3 CH.sub.3                                                 "               23                                           OCl                                                                           ∥|                                                     34   CH.sub.3 --C--C=NOCONHCH.sub.2 CH.sub.2 Cl                                                     "               24                                           OCl                                                                           ∥|                                                     35   (CH.sub.3).sub.2 CH--C--C=NOCONHCH.sub.3                                                       "               25                                           OCl                                                                           ∥|                                                     36   C--C=NOCONHCH.sub.3                                                                            "               26                                           OCl                                                                           ∥|                                                     37   (CH.sub.3).sub.3 --C--C=NOCONHCH.sub.3                                                         "               27                                           OCl                                                                           ∥|                                                     38   CH.sub.3 --C--C=NOCONHCH.sub.3                                                                 BrCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2.2HB                          r               28                                           OCl                                                                           ∥|                                                     39   CH.sub.3 C--C=NOCON(CH.sub.3).sub.2                                                            "               29                                      __________________________________________________________________________

EXAMPLE 40

Compound No. 36 was prepared in the following manner: A suspension of2.28 g. (0.01 mole) of Compound No. 31 in 40 ml. of dichloromethane wascooled to 0°C. and treated with 1.39 ml. (1.01 g., 0.01 mole) oftriethylamine. A solution of 0.79 ml. (1.13 g., 0.01 mole) ofchloroacetyl chloride in 5 ml. of dichloromethane was then addeddropwise, the reaction temperature being maintained at 0°C. After themixture was allowed to warm to room temperature the solvent wasevaporated. The residue was taken up in tetrahydrofuran and the aminesalt removed by filtration. Evaporation of the solvent from the filtrateproduced 3.8 g. of oil which was purified by chromatography overFlorisil (20 g. packed in benzene) using chloroform as the elutingsolvent. The product fractions were evaporated to dryness giving 0.94 g.of Compound No. 36 as a colorless oil. Alternatively the product couldbe purified by extraction of a benzene-dichloromethane (2:1) solutionthereof with water followed by drying and concentrating the organicphase.

EXAMPLE 41

Compound No. 35 was prepared according to the procedure of Example 40,except that CH₃ COCl was used instead of chloroacetyl chloride.

EXAMPLE 42

Compound No. 37 was prepared according to the procedure of Example 40except that CH₃ NCO was used instead of chloroacetyl chloride.

EXAMPLE 43

Compound No. 38 was prepared in the following manner: A mixture of 5.0g. (0.027 mole) of Compound No. 1 and 4.0 g. (0.027 mole) of chloral in30 ml. of benzene was stirred 12 hours at room temperature and filteredproviding 8.7 g. (97%) of Compound No. 38 as a white solid, m.p.155°-156°C.

EXAMPLE 44

Compound No. 39 was prepared according to the procedure of Example 43,except that Compound No. 2 (instead of Compound No. 1) was treated withchloral as set forth therein.

EXAMPLE 45

Compound No. 45 was prepared as follows: A solution of 3.0 g. (0.0134mole) of Compound No. 40 in 30 ml. of chloroform was cooled to 0°C. andtreated cautiously with a solution of 1.4 g. of chlorine in 20 ml. ofchloroform at 0°C. After the excess chlorine as removed, the reactionmixture was cooled to 5°C. and 20 g. of potassium carbonate was addedfollowed by 5 ml. of water. The mixture was then filtered and evaporatedto dryness leaving 3.8 g. of syrup which was purified by dissolving in 8ml. of ethyl acetate and passing through a chromatographic columncontaining 40 g. of silica gel. The product was eluted with ethylacetate-methanol (20:1). Evaporation of the solvent gave 1.4 g. ofCompound No. 45 as a waxy semi-solid.

EXAMPLE 46

Compound No. 46 was prepared according to the procedure of Example 45,except that Compound 42 (instead of Compound No. 40) was treated withchlorine as set forth therein.

EXAMPLE 47

Compound No. 47 was prepared as follows: A solution of 5.0 g. (0.027mole) of Compound No. 1 in 100 ml. of ethyl acetate was saturated withanhydrous hydrogen chloride. The resulting suspension was filtered andthe hygroscopic solid dried in a vacuum desiccator affording 5.9 g.(99%) of Compound No. 47 as a cream-colored solid, m.p. 150°-155°C.

EXAMPLE 48

Compound No. 48 was prepared according to the procedure of Example 47except that Compound No. 19 (instead of Compound No. 1) was treated withanhydrous hydrogen chloride.

EXAMPLE 49

Compound No. 49 was prepared as follows: A solution of 1.0 g. ofCompound No. 1 in 5 ml. of ethyl acetate (or acetonitrile) and 2 ml. ofmethyl iodide was stirred overnight at room temperature, diluted withethyl ether and the precipitated solid collected by filtration yielding1.5 g. of Compound No. 49 as a light yellow solid, m.p. 185°-190°C.

EXAMPLE 50

Compound No. 50 was prepared according to the procedure of Example 49,except that Compound No. 19 (instead of Compound No. 1) was treated withmethyl iodide as set forth therein.

EXAMPLE 51

Compound No. 51 was prepared by the procedure of Example 49, except thatCompound 19 (instead of Compound No. 1) was treated with C₆ H₅ CH₂ Br.

EFFICACY

The insecticidal and acaricidal activities of representative and typicaloxime carbamates of this invention were determined according to thefollowing described methods.

Test formulations of candidate samples were prepared by dissolving eachcandidate compound in acetone containing small amounts of emulsifier.The test formulations (solutions) were then diluted with water to obtainthe desired active ingredient concentration. Where solubility was aproblem, the diluted test formulation was wet ball-milled.

EXAMPLES 52-153A TEST ORGANISMS

Southern Armyworm -- (Prodenia eridania), and Mexican Bean Beetle --(Epilachna varivestis)

Lima bean leaves dipped into test solutions of the respective compoundswere offered to ten larvae of the Southern Armyworm (late third instar)and the Mexican Bean Bettle (late second instar) for a 48-hour feedingperiod. Mortality data were recorded. In these tests, as in testsagainst all other organisms, untreated controls were included forcomparative purposes.

Tables 4 and 5 summarize the activity of the indicated oxime carbamatesagainst Southern Armyworms and Mexican Bean Beetles respectively. Blankspaces in these subsequent Tables mean that no tests were conducted atthe corresponding particular concentrations.

                  TABLE 4                                                         ______________________________________                                        Test Organism: Southern Armyworm (Prodenia eridania)                                             Percent Mortality                                          Example Compound   Application Concentration                                  No.     No.        0.1     0.05   0.01  0.005                                 ______________________________________                                        52      1          100     100    0                                           53      2          0                                                          54      3          0                                                          55      4          0                                                          56      5          0                                                          57      6          40                                                         58      7          0                                                          59      8          100     100    90    40                                    60      9          100     100    20                                          61      10         100     100    0                                           62      11         100     90     0                                           63      12         80                                                         64      13         90      90     10                                          65      14         0                                                          66      15         0                                                          67      16         100     100    80    50                                    68      17         60                                                         69      18         70                                                         70      19         100     100    70    40                                    71      20         40                                                         72      21         30                                                         73      22         0                                                          74      23         0                                                          75      24         0                                                          76      25         0                                                          77      26         0                                                          78      27         0                                                          79      28         100     80     60    0                                     80      29         0                                                          81      30         0                                                          82      31         50                                                         83      32         0                                                          84      33         0                                                          85      34         0                                                          86      35         0                                                          87      36         0                                                          88      37         0                                                          89      38         0                                                          90      39         0                                                          91      40         100     90     0                                           92      41         0                                                          93      42         100     100    60    20                                    94      43         0                                                          95      44         0                                                          96      45         0                                                          97      46         10                                                         98      47         50                                                         99      48                                                                    100     49         100     80     0                                           101     50         100     60     0                                           102     51         0                                                          102A    52         60                                                         Untreated                                                                             --         0       0      0     0                                     ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________    Test Organism: Mexican Bean Beetle (Epilachna varivestis)                                 Percent Mortality                                                 Example                                                                             Compound                                                                            Application Concentration                                         No.   No.   0.1 0.05                                                                              0.01                                                                              0.005                                                                              0.001                                                                              0.0005                                      __________________________________________________________________________    103   1     100 90  0                                                         104   2     0                                                                 105   3     0                                                                 106   4     0                                                                 107   5     70                                                                108   6     60                                                                109   7     0                                                                 110   8     100 100 100 100  10                                               111   9     100 100 50                                                        112   10    100 100 100 100  0                                                113   11    100 100 50                                                        114   12    100 90  10                                                        115   13    100 90  70  50                                                    116   14    100 100 50  50                                                    117   15    0                                                                 118   16    100 100 100 90   50                                               119   17    20                                                                120   18    80                                                                121   19    100 100 100 100  80   40                                          122   20    80                                                                123   21    70                                                                124   22    100 40                                                            125   23    0                                                                 126   24    40                                                                127   25    100 20                                                            128   26    0                                                                 129   27    0                                                                 130   28    100 100 60  50                                                    131   29    60                                                                132   30    0                                                                 133   31    0                                                                 134   32    0                                                                 135   33    0                                                                 136   34    0                                                                 137   35    0                                                                 138   36    0                                                                 139   37    0                                                                 140   38    0                                                                 141   39    0                                                                 142   40    100 100 40  20                                                    143   41    70                                                                144   42    100 100 100 100  40                                               145   43    80                                                                146   44    0                                                                 147   45    0                                                                 148   46    80                                                                149   47    80                                                                150   48                                                                      151   49    70                                                                152   50    0                                                                 153   51    0                                                                  153A 52    100 20                                                            Untreated                                                                           --    0   0   0   0    0    0                                           __________________________________________________________________________

EXAMPLES 154-255A

Test Organism -- Pea Aphid -- (Macrosiphum pisi)

Contact Test

Ten adult pea aphids were sprayed with representative compounds of thisinvention diluted to the desired concentration and transferred tosimilarly sprayed pea plants. After a culture period of 48 hours,mortality determinations were made. The results are set forth in Table6.

Systemic Test

To the vermiculite substratum of potted pea seedlings there is applied25 ml. of the candidate chemical which has been diluted in a suitablenon-phytotoxic solvent. Three days after treatment the pea plants areinfested with ten adult pea aphids (Macrosiphum pisi). Mortalitydeterminations are made after five days. The results are set forth inTable 7.

                                      TABLE 6                                     __________________________________________________________________________    Test Organism: Pea Aphid (contact) (Macrosiphum pisi)                                     Percent Mortality                                                 No.   No.   0.1 0.05                                                                              0.01                                                                              0.005                                                                              0.001                                                                              0.0005                                                                             0.0001                                                                             0.00005                                                                            0.00001                      __________________________________________________________________________    154   1     100 100 100 20                                                    155   2     100 100 50                                                        156   3     60                                                                157   4     0                                                                 158   5     90  20                                                            159   6     100 100 20                                                        160   7     40                                                                161   8     100 100 50                                                        162   9     100 100 100 100  50                                               163   10    100 100 100 100  30                                               164   11    100 100 100 100  100  100  100  40                                165   12    100 100 100 100  100  90   30   30                                166   13    100 100 100 100  100  70   50                                     167   14    100 100 100 50                                                    168   15    100 100 80  40                                                    169   16    100 100 100 100  100  100  50                                     170   17    100 100 100 100  100  90   20                                     171   18    100 100 100 40                                                    172   19    100 100 100 100  100  100  80   15                                173   20    100 100 100 100  100  100  100  40                                174   21    100 100 100 100  70   50   20                                     175   22    100 100 100 30                                                    176   23    100 80  60  10                                                    177   24    100 100 100 100  0                                                178   25    100 100 60                                                        179   26    20                                                                180   27    100 80  0                                                         181   28    100 100 100 100  100  100  50                                     182   29    100 100 100 100  100  40                                          183   30    30                                                                184   31    100 100 60                                                        185   32    100 100 30                                                        186   33    100 40  0                                                         187   34    100 100 50                                                        188   35    100 100 100 10                                                    189   36    100 100 60                                                        190   37    100 50  0                                                         191   38    10                                                                192   39    0                                                                 193   40    100 100 100 100  100  100  50                                     194   41    100 80  50                                                        195   42    100 100 100 100  30                                               196   43    100 100 100 100  100  30                                          197   44    80                                                                198   45    100 100 100 60                                                    199   46    100 100 100 40                                                    200   47    100 100 60                                                        201   48                     100  100  50                                     202   49    10                                                                203   50    90  60  0                                                         204   51    100 100 90  50                                                     204A 52    100 100 100 100  100  100  100  100                               Untreated                                                                           --    0   0   0   0    0    0    0    0                                 __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    Test Organism: Pea Aphid (Systemic) (Macrosiphum pisi)                                    Percent Mortality                                                 Example                                                                             Compound                                                                            Application Concentration                                         No.   No.   0.1 0.05                                                                              0.01                                                                              0.005                                                                              0.001                                                                              0.0005                                                                             0.0001                                 __________________________________________________________________________    205   1     100 100 40                                                        206   2     0                                                                 207   3     0                                                                 208   4     0                                                                 209   5     0                                                                 210   6     0                                                                 211   7     0                                                                 212   8     0                                                                 213   9     100     0                                                         214   10    0                                                                 215   11    100 100 100 20                                                    216   12    100         100  50                                               217   13    100         100  0                                                218   14    100         40   10                                               219   15    0                                                                 220   16    100         60   0                                                221   17    100         100  0    0                                           222   18    80                                                                223   19    100 100 100 0                                                     224   20    100 100 100 100  100  40                                          225   21    100     0                                                         226   22    0                                                                 227   23    0                                                                 228   24    0                                                                 229   25    0                                                                 230   26    0                                                                 231   27    0                                                                 232   28    100 100 40  0                                                     233   29    100     100 10   0                                                234   30    0                                                                 235   31    0                                                                 236   32    0                                                                 237   33    0                                                                 238   34    0                                                                 239   35    0                                                                 240   36    0                                                                 241   37    0                                                                 242   38    0                                                                 243   39    0                                                                 244   40    100     100 60   30                                               245   41    0                                                                 246   42    100     100 100  0                                                247   43    100     90  60   0                                                248   44    0                                                                 249   45    0                                                                 250   46    90          0                                                     251   47    60                                                                252   48                                                                      253   49    10                                                                254   50    0                                                                 255   51    0                                                                  255A 52    100         100  100  100  10                                     Untreated                                                                           --    0   0   0   0    0    0    0                                      __________________________________________________________________________

EXAMPLES 256-306A

Strawberry Mite -- (Tetranychus atlanticus)

Excised lima bean plants were infested with 50 to 100 adults of thestrawberry spider mite prior to testing. The infested plants were dippedinto water dilutions of each test chemical. Treated test plants wereallowed to dry and then cultured at room temperature. After 5 days,mortality counts were made. The results are noted in Table 8.

EXAMPLES 307-357A

Housefly -- (Musca domestica)

Diluted samples were applied to houseflies in a contact test by means ofthe Waters vertical spray tower. The spray tower is operated at 10 psiand discharges about 28 ml. of material per minute through a glassatomizer. The spray descends through an 8 inch stainless steel cylinderto the plant or test insects 44 inches below the atomizer.

Fifty adult houseflies were sprayed in a 2 inches high by 5 inchesdiameter stainless steel cage faced on top and bottom with 14 meshscreen. The insects were retained in the same cages for knockdownobservations. The 24-hour mortality of houseflies may be from residualas well as from direct contact. The percentages of knockdown and killare summarized in Table 9.

                  TABLE 8                                                         ______________________________________                                        Test Organism: Strawberry Mite (Tetranchus atlanticus)                                           Percent Mortality                                          Example Compound   Application Concentration                                  No.     No.        0.1     0.05   0.01  0.005                                 ______________________________________                                        256     1          68      17                                                 257     2          0                                                          258     3          0                                                          259     4          0                                                          260     5          0                                                          261     6          0                                                          262     7          0                                                          263     8          34                                                         264     9          22                                                         265     10         21                                                         266     11         100     20     0                                           267     12         86                                                         268     13         35                                                         269     14         15                                                         270     15         12                                                         271     16         76                                                         272     17         100     43                                                 273     18         54                                                         274     19         100     40     33    30                                    275     20         73                                                         276     21         20                                                         277     22         0                                                          278     23         0                                                          279     24         21                                                         280     25         0                                                          281     26         0                                                          282     27         0                                                          283     28         90      95     77    30                                    284     29         33                                                         285     30         0                                                          286     31         0                                                          287     32         0                                                          288     33         0                                                          289     34         0                                                          290     35         0                                                          291     36         15                                                         292     37         0                                                          293     38         0                                                          294     39         0                                                          295     40         88      52     10                                          296     41         13                                                         297     42         95      43     25    0                                     298     43         90      45     42    0                                     299     44         0                                                          300     45         10                                                         301     46         83      87     15                                          302     47         64                                                         303     48                                                                    304     49         97      94     35                                          305     50         0                                                          306     51         0                                                           306A   52         86                                                         Untreated                                                                             --         0       0      0     0                                     ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________    Test Organism: Housefly (Musca domestica)                                                 Percent Mortality                                                             Application Concentration                                         Example                                                                             Compound                                                                            0.1     0.05    0.01   0.005  0.001                               No.   No.   KD  Kill                                                                              KD  Kill                                                                              KD Kill                                                                              KD Kill                                                                              KD Kill                             __________________________________________________________________________    307   1     100 100 100 100 0  16                                             308   2     10  10                                                            309   3     0   0                                                             310   4     0   12                                                            311   5     0   0                                                             312   6     100 100 80  100 10 50                                             313   7     0   12 -314                                                                           8   100 100                                                                              100 100                                                                              70  80 30  30                           315   9     72  62                                                            316   10    100 100 100 100 94 100 90 88  0  0                                317   11    100 100 30  96  0  0                                              318   12    80  62                                                            319   13    98  86                                                            320   14    50  58                                                            321   15    0   0                                                             322   16    100 100 100 100 40 28  6  0                                       323   17    90  38                                                            324   18    100 100 90  86  8  10  0  0                                       325   19    100 100 90  82  0  6                                              326   20    6   8                                                             327   21    0   0                                                             328   22    0   0                                                             329   23    0   0                                                             330   24    0   0                                                             331   25    0   0                                                             332   26    0   0                                                             333   27    0   0                                                             334   28    100 100 80  44  0  0   0  0                                       335   29    0   0                                                             336   30    0   0                                                             337   31    0   0                                                             338   32    0   0                                                             339   33    0   0                                                             340   34    0   0                                                             341   35    0   0                                                             342   36    0   0                                                             343   37    0   0                                                             344   38    0   0                                                             345   39    0   90  0   0                                                     346   40    100 100 100 100 30 58  0  8                                       347   41    0   0                                                             348   42    100 100 100 100 40 40  14 12                                      349   43    0   0                                                             350   44    0   0                                                             351   45    0   0                                                             352   46    0   0                                                             353   47    96  100 24  96  0  0                                              354   48                                                                      355   49    30  96  0   0                                                     356   50    0   0                                                             357   51    0   0                                                              357A 52    20  0                                                             Untreated                                                                           --    0   0   0   0   0  0   0  0   0  0                                __________________________________________________________________________

EXAMPLE 357-B

German Cockroach (Blatella germanica)

The procedure for testing against this species was the same as thatemployed for the housefly, except that twenty specimens were utilized(instead of fifty) and observations were made after 48 hours (instead of24). In this test, Compound Nos. 9-10, 12-18, 21-22, 24, 29-30, 33,35-37, 40-46, 48 and 52 were not tested. Compounds 1-8, 11, 19-20, 23,25, 26-28, 31-32, 34, 38-39, 47, 49-51 were tested at a concentration of0.1%, with the result that the only activity displayed was by CompoundNo. 11 which showed a 20% mortality.

EXAMPLES 358-382

Corn Earworm (Heliothis zea)

The procedure for testing against this species was the same as thatemployed for the Southern Armyworm. The Compounds tested were CompoundNos. 1-8, 11, 19-20, 23, 25-28, 31-32, 34, 38-39, 47, 49-51. The resultsare set forth in Table 10.

                  TABLE 10                                                        ______________________________________                                        Test Organism: Corn Earworm (Heliothis zea)                                                      Percent Mortality                                          Example Compound   Application Concentration                                  No.     No.        0.1     0.05   0.01  0.005                                 ______________________________________                                        358     1          100     50     0                                           359     2          0                                                          360     3          0                                                          361     4          0                                                          362     5          0                                                          363     6          0                                                          364     7          0                                                          365     8          100     20     0                                           366     11         100     20     0                                           367     19         30                                                         368     20         0                                                          369     23         0                                                          370     25         60                                                         371     26         0                                                          372     27         0                                                          373     28         100     70     30    0                                     374     31         0                                                          375     32         0                                                          376     34         0                                                          377     38         0                                                          378     39         0                                                          379     47         0                                                          380     49         40                                                         381     50         40                                                         382     51         0                                                          Untreated                                                                             --         0       0      0     0                                     ______________________________________                                    

As hereinbefore stated, the oxime carbamates of the present inventionare broadly effective as insecticides and acaricides. It should beunderstood, however, that each particular compound of the present oximecarbamate genus, although exhibiting insecticidal and acaricidalactivity as indicated by the foregoing examples, may be not effectiveagainst each and every insect and acarid species.

What is claimed is:
 1. Novel oxime-carbamates of the formula ##SPC7##where R₁ is --CH₃, --CH(CH₃)₂, ##EQU6## --C(CH₃)₃, or --C₆ H₅ ; R₂ is --H or --CH₃ ; R₃ is --CH₃, --CH₂ CH₃, --(CH₂)₂ CH₃, --(CH₂)₃ CH₃, --CH₂ CH₂ Cl or --C₆ H₅ ; R₄ is --H, --CH₃, --CH₂ CH₃, --(CH₂)₂ CH₃, --CH(CH₃)₂, --(CH₂)₃ CH₃, --CH₂ CH=CH₂, --CH₂ C.tbd.CH, --C₆ H₅, ##EQU7## --CH(OH)CCl₃, --CH₂ CH₂ X₁, where X₁ is --Cl, --Br, --NH₂, --OH, --OCOCH₃, --OCOCH₂ Cl, or --OCONHCH₃ ; R₅ and R₆ are each --H or --CH₃, with the proviso that when R₅ and R₆ are both CH₃ then both CH₃ groups may be on either the same carbon atom or on different carbon atoms; R₇ is H, --CH₃ or --CH₂ C₆ H₅ ; X₂ is Cl, --Br or --I; and n is 0 or 1, with the proviso that when n is 1 then Nbears a + charge and X₂ bears a - charge.
 2. The compound of claim 1 wherein R₁ is --CH₃ , R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 3. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 4. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₂ CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 5. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --C₆ H₅, R₄, R₅ and R₆ are each --H, and n is
 0. 6. The compound of claim 1 wherein R₁ is --CH(CH₃)₂, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 7. The compound of claim 1 wherein R₁ is ##EQU8## R₂ is --H, R₃ is --CH₃, and R₄, R₅ and R₆ are each --H, and n is
 0. 8. The compound of claim 1 wherein R₁ is --C₆ H₅, R₂ is --H, R₃ is --CH₃, and R₄, R₅ and R₆ are each --H, and n is
 0. 9. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --H, R₅ is --CH₃, R₆ is --H, and n is
 0. 10. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --H, R₅ and R₆ are each --CH₃, and n is
 0. 11. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ and R₄ are each --CH₃, R₅ and R₆ are each --H, and n is
 0. 12. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 13. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 14. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ and R₄ are each --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 15. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₂ CH₃, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 16. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₂ CH₂ Cl, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 17. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --(CH₂)₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 18. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH(CH₃)₂, R₅ and R₆ are each --H, and n is
 0. 19. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --(CH₂)₃ CH₃, R₅ and R₆ are each --H, and n is
 0. 20. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 21. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 22. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₂ CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 23. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₂ CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 24. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₃ CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 25. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ and R₄ are each --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 26. The compound of claim 1 wherein R₁ is --CH(CH₃)₂, R₂ is --H, R₃ is --CH₃, R₄ is CH₂ CH₂ Cl, R.sub. 5 and R₆ are each --H, and n is
 0. 27. The compound of claim 1 wherein R₁ is ##EQU9## R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 28. The compound of claim 1 wherein R₁ is --C(CH₃)₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 29. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Br, R₅ and R₆ are each --H, and n is
 0. 30. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₂ Br, R₅ and R₆ are each --H, and n is
 0. 31. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ NH₂, R₅ and R₆ are each --H, and n is
 0. 32. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 33. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 34. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₃ CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 35. The compound of claim 1 wherein R₁ is ##EQU10## R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 36. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OCOCH₃, R₅ and R₆ are each --H, and n is
 0. 37. The compound of claim 1 wherein R₁ is --CH₃, R₂ is H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OCOCH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 38. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OCONHCH₃, R₅ and R₆ are each --H, and n is
 0. 39. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH(OH)CCl₃, R₅ and R₆ are each --H, and n is
 0. 40. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH(OH)CCl₃, R₅ and R₆ are each H, and n is
 0. 41. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH=CH₂, R₅ and R₆ are each --H, and n is
 0. 42. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is CH₂ CH=CH₂, R₅ and R₆ are each --H, and n is
 0. 43. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ C .tbd. CH, R₅ and R₆ are each --H, and n is
 0. 44. The compound of claim 1 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ C.tbd.CH, R₅ and R₆ are each --H, and n is
 0. 45. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --C₆ H₅, R₅ and R₆ are each --H, and n is
 0. 46. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is ##EQU11## R₅ and R₆ are each --H, and n is
 0. 47. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is ##EQU12## R₅ and R₆ are each --H, and n is
 0. 48. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, R₇ is --H, X₂ is --Cl, and n is
 1. 49. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, R₇ is --H, X₂ is --Cl, and n is
 1. 50. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, R₇ is --CH₃, X₂ is --I, and n is
 1. 51. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃ , R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, R₇ is --CH₃, X₂ is --I, and n is
 1. 52. The compound of claim 1 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, R₇ is --CH₂ C₆ H₅, X₂ is --Br, and n is
 1. 53. The compound of claim 1 wherein R₁, R₂, and R₃ are each --CH₃, R₄ is --(CH₂)₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 54. A process for control of insect and acarid infestation which comprises applying either to the locus of said infestation or systemically a pecticidally effective amount of an oxime carbamate of the general formula ##SPC8##where R₁ is --CH₃, --CH(CH₃)₂, ##EQU13## --C(CH₃)₃, or --C₆ H₅ ; R₂ is --H or --CH₃ ; R₃ is --CH₃, --CH₂ CH₃, --(CH₂)₂ CH₃, --(CH₂)₃ CH₃, --CH₂ CH₂ Cl or --C₆ H₅, R₄ is --H, --CH₃, --CH₂ CH₃, --(CH₂)₂ CH₃, --CH(CH₃)₂, --(CH₂)₃ CH₃, --CH₂ CH=CH₂, --CH₂ C.tbd.CH, --C₆ H₅, ##EQU14## --CH(OH)CCl₃, --CH₂ CH₂ X₁, where X₁ is --Cl, --Br, --NH₂, --OH, --OCOCH₃, --OCOCH₂ Cl, or --OCONHCH₃ ; R₅ and R₆ are each --H or --CH₃, with the proviso that when R₅ and R₆ are both CH₃ then both CH₃ groups may be on either the same carbon atom or on different carbon atoms; R₇ is H, --CH₃ or --CH₂ C₆ H₅ X₂ is --Cl, --Br or --I; and n is 0 or 1, with the proviso that when n is 1 then Nbears a + charge and X₂ bears a - charge.
 55. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 56. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 57. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₂ CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 58. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --C₆ H₅, R₄, R₅ and R₆ are each --H, and n is
 0. 59. The process of claim 54 wherein R₁ is --CH(CH₃)₂, R₂ is --H, R₃ is --CH₃, and R₄, R₅ and R₆ are each --H, and n is
 0. 60. The process of claim 54 wherein R₁ is ##EQU15## R₂ is --H, R₃ is --CH₃, and R₄, R₅ and R₆ are each --H, and n is
 0. 61. The process of claim 54 wherein R₁ is --C₆ H₅, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, and n is
 0. 62. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --H, R₅ is --CH₃, R₆ is --H, and n is
 0. 63. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --H, R₅ and R₆ are each --CH₃, and n is
 0. 64. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ and R₄ are each --CH₃, R₅ and R₆ are each --H, and n is
 0. 65. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 66. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 67. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ and R₄ are each --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 68. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₂ CH₃, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 69. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₂ CH₂ Cl, R₄ is --CH₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 70. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --(CH₂)₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 71. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH(CH₃)₂, R₅ and R₆ are each --H, and n is
 0. 72. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --(CH₂)₃ CH₃, R₅ and R₆ are each --H, and n is
 0. 73. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 74. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each H, and n is
 0. 75. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₂ CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 76. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₂ CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 77. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₃ CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 78. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ and R₄ are each --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 79. The process of claim 54 wherein R₁ is --CH(CH₃)₂, R₂ is --H, R₃ is --CH₃, R₄ is CH₂ CH Cl, R₅ and R₆ are each --H, and n is
 0. 80. The process of claim 54 wherein R₁ is ##EQU16## R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 81. The process of claim 54 wherein R₁ is --C(CH₃)₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, and n is
 0. 82. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Br, R₅ and R₆ are each --H, and n is
 0. 83. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₂ Br, R₅ and R₆ are each --H, and n is
 0. 84. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ NH₂, R₅ and R₆ are each --H, and n is
 0. 85. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 86. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 87. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --(CH₂)₃ CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 88. The process of claim 54 wherein R₁ is ##EQU17## R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OH, R₅ and R₆ are each --H, and n is
 0. 89. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OCOCH₃, R₅ and R₆ are each --H, and n is
 0. 90. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OCOCH₂ Cl, R.sub. 5 and R₆ are each --H, and n is
 0. 91. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ OCONHCH₃, R₅ and R₆ are each --H, and n is
 0. 92. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH(OH)CCl₃, R₅ and R₆ are each --H, and n is
 0. 93. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH(OH)CCl₃, R₅ and R₆ are each H, and n is
 0. 94. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH=CH₂, R₅ and R₆ are each --H, and n is
 0. 95. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is CH₂ CH=CH₂, R₅ and R₆ are each --H, and n is
 0. 96. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ C.tbd.CH, R₅ and R₆ are each --H, and n is
 0. 97. The process of claim 54 wherein R₁, R₂ and R₃ are each --CH₃, R₄ is --CH₂ C.tbd.CH, R₅ and R₆ are each --H, and n is
 0. 98. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --C₆ H₅, R₅ and R₆ are each --H, and n is
 0. 99. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is ##EQU18## R₅ and R₆ are each --H, and n is
 0. 100. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is ##EQU19## R₅ and R₆ are each --H, and n is
 0. 101. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, R₇ is --H, X₂ is --Cl, and n is
 1. 102. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, R₇ is --H, X₂ is --Cl, and n is
 1. 103. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄, R₅ and R₆ are each --H, R₇ is --CH₃, X₂ is --I, and n is
 1. 104. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, R₇ is --CH₃, X₂ is --I, and n is
 1. 105. The process of claim 54 wherein R₁ is --CH₃, R₂ is --H, R₃ is --CH₃, R₄ is --CH₂ CH₂ Cl, R₅ and R₆ are each --H, R₇ is --CH₂ C₆ H₅, X₂ is --Br, and n is
 1. 106. The process of claim 54 wherein R₁, R₂, and R₃ are each --CH₃, R₄ is --(CH₂)₂ CH₃, R₅ and R₆ are each --H, and n is
 0. 